Diels-alder Reactions With 2-substituted-alpha,Beta-unsaturated Hydrazones in Concentrated Organic Solutions of Lintf2

alpha,beta-Unsaturated hydrazones bearing an ester or a nitrile at C-2 position have been synthesized. They are unreactive towards electron-rich dienophiles but react with electron-poor dienophiles. Dramatic rate enhancements have been observed in concentrated organic solutions of LiNTf(2)

Amine Directed Palladium Catalyzed C‐H Halogenation of Phenylalanine Derivatives

International audienceAn efficient primary amine-directed palladium catalyzed C-H halogenation (X = I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suited conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA

Copper‐Photocatalyzed Borylation of Organic Halides under Batch and Continuous‐Flow Conditions

International audienceThe copper‐photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic‐acid esters in good to excellent yields. The reaction was extended to continuous‐flow conditions to allow an easy scale‐up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested

Base-Assisted Intramolecular C–N Coupling Reaction from NH 2 -Bound Cyclopalladated L -Phenylalanine to Indoline-2-carboxylic Acid

International audienceThe deprotonative intramolecular-amination reaction of phenylalanine-derived palladacycles has been investigated to highlight a facile carbonate-assisted N–H activation before the C–N bond formation. A major counterion effect led to divergent pathways whereby the SPhos-Pd complexes with iodine, triflate, or trifluoroacetate anions were key intermediates to afford access to (S)-2-indolinecarboxylic acid derivatives